CN113130897B - Water-based binder and preparation method and application thereof - Google Patents
Water-based binder and preparation method and application thereof Download PDFInfo
- Publication number
- CN113130897B CN113130897B CN202010036091.XA CN202010036091A CN113130897B CN 113130897 B CN113130897 B CN 113130897B CN 202010036091 A CN202010036091 A CN 202010036091A CN 113130897 B CN113130897 B CN 113130897B
- Authority
- CN
- China
- Prior art keywords
- amino
- self
- gas
- carbon material
- repairing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to the technical field of batteries, and particularly relates to a preparation method of a water-based binder, which comprises the following steps: obtaining an amino-terminated polymer and a diisocyanate modified monomer, dissolving the amino-terminated polymer and the diisocyanate modified monomer in an organic solvent, and then carrying out a mixing reaction to obtain a solution of self-repairing molecules; obtaining a dispersion liquid of a carbon material, mixing the dispersion liquid of the carbon material with the solution of the self-repairing molecules, carrying out heat treatment, and drying to obtain a water-based binder solid product; wherein the carbon material contains an active group capable of being connected with the self-repairing molecule. The aqueous binder prepared by the invention not only has proper viscosity, but also can effectively inhibit the volume expansion of the electrode material, relieve the problems of pole piece pulverization, active material peeling and the like caused by the volume expansion of the electrode material, improve the strength of the battery pole piece and the electron transmission capability in the pole piece, and improve the safety and the cycling stability of the battery.
Description
Technical Field
The invention belongs to the technical field of batteries, and particularly relates to a water-based binder and a preparation method thereof, a lithium ion battery negative plate and a lithium ion battery.
Background
Lithium ion batteries have been rapidly developed due to their high specific energy, no pollution, and a wide range of applications, and have been expanded from mobile communication power supplies, notebook computers, cameras, and the like to the fields of electric tools, electric vehicles, and the like. The commercial graphite materials in the existing lithium ion battery system are close to the theoretical specific capacity (372 mAh/g), and a battery system with higher energy density must be developed to further promote the development of electric automobiles. The silicon-based material has the advantages of high electrochemical reversible capacity, good safety, abundant resources and the like, is a preferred material of the cathode material of the lithium ion secondary battery, and is considered as the most potential battery cathode material. However, the silicon-based negative electrode faces a serious volume change problem in the charging and discharging process, and the contact between particles and a binder is deteriorated due to internal stress caused by the severe volume change, so that the problems of electrode pulverization, active material peeling and the like are caused, and irreversible damage is caused to the performance of the battery. There is therefore a need to develop a binder that is stable and compatible with the anode material, while at the same time being able to stabilize the electrode structure during cycling.
Compared with an organic binder, the aqueous binder does not contain highly toxic and volatile organic solvents, is green and environment-friendly, has lower cost, is non-combustible and high in safety, and is an important development direction of the conventional cathode binder. At present, the mature commercial water system binder comprises Styrene Butadiene Rubber (SBR), sodium carboxymethylcellulose (CMC) and the like, but the inhibiting and protecting effects on the expansion of particles in the circulating process are not ideal. In some prior arts, it is proposed to apply a terpene resin-based aqueous binder to a negative electrode of a lithium ion battery or a supercapacitor, and although the rate capability and the cycle stability of the battery can be improved, the swelling of particles is not well inhibited. In other prior arts, a method of applying a hydrophobically modified natural plant polysaccharide aqueous binder to a lithium ion battery has been proposed, but the method has a less significant effect of inhibiting the particles from being crushed due to volume expansion. Active material particles are pulverized due to huge volume change in the charging and discharging processes, so that a new interface is continuously generated, the new interface reacts with an electrolyte and continuously consumes lithium ions, and the coulomb efficiency of the battery is reduced. Based on the problems that the volume change of the negative electrode causes the adhesion of the particles to the binder to be reduced and the pulverization of the particles to generate new interfaces, the binder capable of effectively inhibiting the expansion of the silicon-based negative electrode particles must be developed.
Disclosure of Invention
The invention aims to provide a preparation method of an aqueous binder, and aims to solve the technical problems that the conventional aqueous binder cannot effectively inhibit the volume expansion of a negative electrode material in the charging and discharging processes, and simultaneously satisfies the characteristics of high cohesiveness, conductivity and the like.
Another object of the present invention is to provide an aqueous adhesive.
The invention further aims to provide a lithium ion battery negative plate.
It is still another object of the present invention to provide a lithium ion battery.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:
a method for preparing a water-based binder, comprising the steps of:
obtaining an amino-terminated polymer and a diisocyanate modified monomer, dissolving the amino-terminated polymer and the diisocyanate modified monomer in an organic solvent, and then carrying out a mixing reaction to obtain a solution of self-repairing molecules;
obtaining a dispersion liquid of a carbon material, mixing the dispersion liquid of the carbon material with the solution of the self-repairing molecules, carrying out heat treatment, and drying to obtain a water-based binder solid product; wherein the carbon material contains an active group capable of being connected with the self-repairing molecule.
Preferably, the amino-terminated polymer is selected from: at least one of amino-terminated polyethylene glycol and amino-terminated polyvinyl alcohol; and/or the presence of a gas in the gas,
the diisocyanate modified monomer is selected from: 1,3-diisocyanatobenzene, hexamethylene diisocyanate, p-phenylene diisocyanate, isophorone diisocyanate; and/or the presence of a gas in the gas,
the organic solvent is selected from: at least one of dimethylacetamide, N-dimethylformamide, acetone and chloroform.
Preferably, the step of dissolving the amino-terminated polymer and the diisocyanate-modified monomer in an organic solvent comprises: according to the mass ratio of the amino-terminated polymer to the diisocyanate modified monomer (8-12): 1, dissolving the amino-terminated polymer and the diisocyanate-modified monomer in an organic solvent; and/or the presence of a gas in the gas,
the conditions of the mixing reaction include: reacting for more than 10 hours at the temperature of 70-90 ℃.
Preferably, the step of mixing and reacting the amino-terminated polymer and the diisocyanate-modified monomer after dissolving them in an organic solvent comprises: mixing the organic solution of the amino-terminated polymer with the organic solution of the diisocyanate modified monomer to form a mixed solution, and reacting at 70-90 ℃ for more than 10 hours; in the mixed solution, the mass ratio of the amino-terminated polymer to the diisocyanate-modified monomer is (8-12): 1; and/or the presence of a gas in the gas,
the average molecular weight of the amino-terminated polyethylene glycol is 400-100000; and/or the presence of a gas in the gas,
the average molecular weight of the amino-terminated polyvinyl alcohol is 400-100000; and/or the presence of a gas in the gas,
the carbon material includes: at least one of carbon nanotubes, graphene and carbon fibers; and/or the presence of a gas in the gas,
the reactive group includes: at least one of a hydroxyl group and a carboxyl group; and/or the presence of a gas in the atmosphere,
the solvent in the dispersion of the carbon material includes: at least one of dimethylacetamide, N-dimethylformamide, acetone and chloroform.
Preferably, the step of mixing the dispersion of carbon material with the solution of self-healing molecules comprises: according to the mass ratio of the functional carbon material to the self-repairing molecule being (1-10): (90-99) mixing the dispersion of the carbon material with the solution of the self-healing molecules; and/or the presence of a gas in the gas,
the conditions of the heat treatment include: reacting for more than 60 minutes at the temperature of 110-130 ℃.
Preferably, the viscosity of the aqueous binder slurry formed after dissolving the aqueous binder solid product in water is in the range of 1000 to 10000mpa.s.
Correspondingly, the water-based binder comprises a carbon material and self-repairing molecules grafted on the surface of the carbon material, wherein the self-repairing molecules are prepared by condensation reaction of an amino-terminated polymer and a diisocyanate modified monomer.
Preferably, the amino-terminated polymer is selected from: at least one of amino-terminated polyethylene glycol and amino-terminated polyvinyl alcohol; and/or the presence of a gas in the gas,
the average molecular weight of the amino-terminated polymer is 400-100000; and/or the presence of a gas in the gas,
the diisocyanate modified monomer is selected from: 1,3-diisocyanatobenzene, hexamethylene diisocyanate, p-phenylene diisocyanate, isophorone diisocyanate; and/or the presence of a gas in the atmosphere,
the carbon material includes: at least one of carbon nanotubes, graphene, carbon fibers; and/or the presence of a gas in the gas,
in the aqueous binder, the mass percentage of the carbon material is 1-10%.
Correspondingly, the lithium ion battery negative plate comprises the aqueous binder prepared by the method or comprises the aqueous binder.
Correspondingly, the lithium ion battery comprises the aqueous binder prepared by the method, or comprises the aqueous binder, or comprises the lithium ion battery negative plate.
The preparation method of the water-based binder provided by the invention takes the amino-terminated polymer with high binding degree and the diisocyanate-modified monomer as raw materials, the amino-terminated polymer and the diisocyanate-modified monomer are obtained through condensation reaction after the two are mixed and are condensed and polymerized to generate the composite molecule, and the composite molecule has the self-repairing characteristic through the intermolecular hydrogen bonding effect because stronger hydrogen bonding effect exists between the carbodiimide groups formed by condensation in the composite molecule; then the self-repairing molecules are condensed with carbon materials containing active groups to prepare the water-based binder. On one hand, when the electrode active material particles expand, self-repairing molecules in the binder form a high-elasticity space on the surfaces of the electrode active material and the conductive agent through the flexible and stretchable intermolecular hydrogen bond action, so that the aqueous binder adapts to the volume change of the electrode in the charging and discharging processes, the binder, the electrode active material and the conductive agent are always kept to be tightly combined, and the electrode material is prevented from falling off; on the other hand, the self-repairing molecules in the binder form a three-dimensional network structure through intermolecular and intramolecular association generated by hydrogen bonds among self-repairing molecular chains connected to the carbon material, and the three-dimensional network structure enhances the capacity of the binder for capturing fragments of the electrode active material, thereby improving the electrochemical properties of the battery, such as stability, safety and the like; on the other hand, the introduction of the carbon material in the binder not only enhances the conductivity of the binder and improves the rigidity of the binder on the basis of the flexibility of self-repairing molecules, thereby improving the strength of a battery pole piece and the electron transmission capacity in the pole piece, but also the flaky or linear carbon material with high specific surface area can play a role in coating the electrode active material, further inhibiting the volume expansion of the electrode active material in the charging and discharging process of the battery, improving the property of the battery pole piece, improving the cycle stability of the battery and prolonging the service life of the battery.
The water-based binder provided by the invention comprises a carbon material and self-repairing molecules grafted on the surface of the carbon material, wherein the self-repairing molecules are prepared by condensation reaction of an amino-terminated polymer and a diisocyanate-modified monomer. The self-repairing molecules in the binder can keep the tight combination between the binder and the electrode active material and the conductive agent through the flexible and telescopic intermolecular hydrogen bond action, so that the electrode material is prevented from falling off due to volume expansion, a three-dimensional network structure can be formed, the capacity of capturing fragments of the electrode active material by the binder is enhanced, and the stable safety of the battery is improved. The carbon material in the adhesive is used as a matrix of self-repairing molecules, so that the conductivity of the adhesive is enhanced, the rigidity of the adhesive is improved, the electrode active material can be coated, the volume expansion of the electrode active material is further inhibited, the cycling stability of the battery is improved, and the service life of the battery is prolonged. The aqueous adhesive disclosed by the invention not only has proper viscosity, but also can effectively inhibit severe volume change of an electrode material, especially a silicon-based negative electrode material, in the charging and discharging processes, relieve the problems of pole piece pulverization, active material peeling and the like caused by internal stress generated by the volume change of the silicon-based material, improve the strength of a battery pole piece and the electron transmission capacity in the pole piece, and improve the safety and the cycling stability of the battery.
The lithium ion battery negative plate provided by the invention contains the aqueous binder which has proper viscosity, rigidity and conductivity and has an inhibiting effect on the volume expansion of the electrode active substance, so that the strength of the lithium ion battery negative plate is improved, the electron transmission capability in the negative plate is improved, and the safety and the cycle stability of the battery are improved.
The lithium ion battery provided by the invention contains the aqueous binder which has proper viscosity, rigidity and conductivity and has an effect of inhibiting the volume expansion of the electrode active material, or contains the lithium ion battery negative plate with excellent stability, strength and electron transmission capability, so that the provided lithium ion battery has the advantages of good safety, good cycle stability and long service life.
Drawings
Fig. 1 is a schematic structural view of a water-based adhesive according to an embodiment of the present invention.
FIG. 2 is a graph showing the viscosity change of the aqueous binder of amino terminated polyethylene glycols of different average molecular weights in example 1 of the present invention;
FIG. 3 is a graph showing the tendency of the negative electrode sheet prepared from the aqueous binder containing carbon materials of different contents in example 3 according to the present invention to show the change in peel strength;
FIG. 4 is a first-turn charge-discharge curve of an assembled half cell of example 4 of the present invention;
fig. 5 is a cycle performance test chart of the assembled full cell of example 5 of the present invention.
Detailed Description
In order to make the objects, technical solutions and technical effects of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are clearly and completely described, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments obtained by a person of ordinary skill in the art without making any creative effort in combination with the embodiments of the present invention belong to the protection scope of the present invention.
In the description of the present invention, it is to be understood that the terms "first", "second" and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
The weight of the related components mentioned in the description of the embodiments of the present invention may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, the content of the related components is scaled up or down within the scope disclosed in the description of the embodiments of the present invention as long as it is in accordance with the description of the embodiments of the present invention. Specifically, the weight described in the description of the embodiments of the present invention may be a mass unit known in the chemical field, such as μ g, mg, g, kg, etc.
The embodiment of the invention provides a water-based binder, which comprises a carbon material and self-repairing molecules grafted on the surface of the carbon material, wherein the self-repairing molecules are prepared by condensation reaction of an amino-terminated polymer and a diisocyanate modified monomer.
The water-based binder provided by the embodiment of the invention comprises a carbon material and self-repairing molecules grafted on the surface of the carbon material, wherein the self-repairing molecules are prepared by condensation reaction of an amino-terminated polymer and a diisocyanate-modified monomer. The self-repairing molecules in the binder can keep the tight combination between the binder and the electrode active material and the conductive agent through the flexible and telescopic intermolecular hydrogen bond action, so that the electrode material is prevented from falling off due to volume expansion, a three-dimensional network structure can be formed, the capacity of capturing fragments of the electrode active material by the binder is enhanced, and the stable safety of the battery is improved. The carbon material in the adhesive is used as a matrix of self-repairing molecules, so that the conductivity of the adhesive is enhanced, the rigidity of the adhesive is improved, the electrode active material can be coated, the volume expansion of the electrode active material is further inhibited, the cycling stability of the battery is improved, and the service life of the battery is prolonged. The aqueous adhesive disclosed by the invention not only has proper viscosity, but also can effectively inhibit severe volume change of an electrode material, especially a silicon-based negative electrode material, in the charging and discharging processes, relieve the problems of pole piece pulverization, active material peeling and the like caused by internal stress generated by the volume change of the silicon-based material, improve the strength of a battery pole piece and the electron transmission capacity in the pole piece, and improve the safety and the cycling stability of the battery.
The water-based adhesive provided by the embodiment of the present invention can be produced by the method described in any of the following embodiments. The carbon material, the self-healing molecules, the content ratio of the carbon material and the self-healing molecules, the selection of the polymer having been used for the condensation reaction to obtain the terminal amino group of the self-healing molecules and the diisocyanate-modified monomer, and the preferred cases thereof in the aqueous binder are discussed in detail in the following preparation method, and are not repeated herein for the sake of brevity.
In some embodiments, the amino-terminated polymer is selected from: at least one of amino-terminated polyethylene glycol and amino-terminated polyvinyl alcohol. The amino-terminated polyethylene glycol and the amino-terminated polyvinyl alcohol in the embodiment of the invention have higher viscosity, so that the adhesive has proper adhesive property.
In some embodiments, the amino-terminated polymer has an average molecular weight of 400 to 100000. With the increase of the molecular weight of the polymer, the viscosity of the binder is higher under the same concentration, and the amino-terminated polymer with proper molecular weight and the diisocyanate modified monomer can be reasonably selected as raw materials to prepare the binder according to the requirement of actual conditions on the viscosity of the binder, so that the flexibility is high and the adaptability is wide.
In some embodiments, the diisocyanate-modified monomer is selected from the group consisting of: 1,3-diisocyanatobenzene, hexamethylene diisocyanate, p-phenylene diisocyanate, isophorone diisocyanate; the monomers contain two isocyanate groups, can perform condensation reaction with amino-terminated polymers to generate composite molecules containing carbonyl diamine groups, and the carbonyl diamine groups have stronger hydrogen bond effect among the composite molecules, so that the composite molecules have the self-repairing characteristic, can adapt to volume change in the electrode charging and discharging process, and prevent electrode materials from falling off; moreover, self-repairing molecules form a three-dimensional network structure through hydrogen bond association between self-repairing molecular chains, and the capability of the binding agent for capturing fragments of the electrode active material is enhanced, so that the electrochemical properties of the battery, such as stability, safety and the like, are improved.
In some embodiments, the carbon material comprises: the carbon material such as the carbon nanotube, the graphene and the carbon fiber has a large comparative area, and can coat active substances in the electrode slurry, so that the electrode active materials can be further inhibited from volume expansion in the charging and discharging processes of the battery, the strength of the electrode plate and the electron transmission capacity in the electrode plate are improved, the cycling stability of the battery is improved, and the service life of the battery is prolonged.
In some embodiments, the carbon material is present in the aqueous binder in an amount of 1 to 10% by mass, and the carbon material in the aqueous binder has an optimum balance among rigidity, conductivity, and volume expansion suppression effect on the electrode active material, and if the carbon material content is too low, the binder is not modified well; if the content of the carbon material is too low, the viscosity of the binder is lowered, the moldability is lowered, and the force acting between the electrode active slurry and the current collector is lowered.
In one embodiment, the structure of the self-healing molecules in the aqueous binder may be represented as follows:
wherein x varies with the average molecular weight of the amino-terminated polyethylene glycol, and when the average molecular weight of the adopted amino-terminated polyethylene glycol is large, the value of x is large, and correspondingly, when the average molecular weight of the adopted amino-terminated polyethylene glycol is small, the value of x is small.
Accordingly, the embodiment of the invention provides a preparation method of a water-based binder, which comprises the following steps:
s10, obtaining an amino-terminated polymer and a diisocyanate modified monomer, dissolving the amino-terminated polymer and the diisocyanate modified monomer in an organic solvent, and then carrying out a mixing reaction to obtain a self-repairing molecule;
s20, obtaining a dispersion liquid of a carbon material, mixing the dispersion liquid of the carbon material with the solution of the self-repairing molecules, performing heat treatment, and drying to obtain a water-based binder solid product;
wherein the carbon material contains an active group capable of being connected with the self-repairing molecule.
The preparation method of the water-based binder provided by the embodiment of the invention takes the amino-terminated polymer with high binding degree and the diisocyanate-modified monomer as raw materials, the amino-terminated polymer and the diisocyanate-modified monomer are obtained through condensation reaction after being mixed and are condensed and polymerized to generate the composite molecules, and the composite molecules have the self-repairing characteristic through the intermolecular hydrogen bonding effect because stronger hydrogen bonding effect exists between the carbodiimide groups formed by condensation in the composite molecules; then the self-repairing molecules are condensed with carbon materials containing active groups to prepare the water-based binder. According to the water-based binder prepared by the embodiment of the invention, on one hand, when electrode active material particles expand, self-repairing molecules in the binder form a high-elasticity space on the surfaces of the electrode active material and the conductive agent through the flexible telescopic intermolecular hydrogen bond action, so that the binder adapts to volume change in the electrode charging and discharging process, the tight combination between the binder and the electrode active material and the conductive agent is always kept, and the electrode material is prevented from falling off; on the other hand, the self-repairing molecules in the binder form a three-dimensional network structure through intermolecular and intramolecular association generated by hydrogen bonds among self-repairing molecular chains connected to the carbon material, and the three-dimensional network structure enhances the capacity of the binder for capturing fragments of the electrode active material, thereby improving the electrochemical properties of the battery, such as stability, safety and the like; on the other hand, the introduction of the carbon material in the binder not only enhances the conductivity of the binder and improves the rigidity of the binder on the basis of the flexibility of self-repairing molecules, thereby improving the strength of a battery pole piece and the electron transmission capacity in the pole piece, but also the flaky or linear carbon material with high specific surface area can play a role in coating the electrode active material, further inhibiting the volume expansion of the electrode active material in the charging and discharging processes of the battery, improving the property of the battery pole piece, improving the cycle stability of the battery and prolonging the service life of the battery.
In some embodiments, the aqueous binder prepared in the embodiments of the present invention may be applied to any battery system requiring an aqueous binder, and can achieve a good binding effect, and at the same time, suppress volume expansion of an electrode active material during charging and discharging, improve battery safety and cycle stability, and further improve conductivity of the electrode material. In some specific embodiments, the aqueous binder prepared by the embodiment of the invention is especially suitable for a lithium ion battery negative electrode slurry containing a silicon-based negative electrode material, can effectively inhibit severe volume change of the silicon-based negative electrode material in the charging and discharging process, relieves the problems of pole piece pulverization, active material peeling and the like caused by internal stress generated by volume change of the silicon-based material, and improves the characteristics of the battery such as safety, cycle stability, conductivity and the like.
Specifically, in step S10, an amino-terminated polymer and a diisocyanate-modified monomer are obtained, and the amino-terminated polymer and the diisocyanate-modified monomer are dissolved in an organic solvent and then mixed to react, so as to obtain a self-repairing molecule. According to the embodiment of the invention, the polymer containing terminal amino and the diisocyanate modified monomer are dissolved in the organic solvent, and the self-repairing molecule is formed by condensation polymerization of the raw material polymer and the monomer through condensation reaction of the raw material polymer and the monomer. The amino-terminated polymer is a high-viscosity polymer molecule, so that the adhesive has high adhesion, and the amino group in the polymer can perform condensation reaction with the isocyanate group in the monomer, so that the polymer and the monomer are subjected to condensation polymerization to generate the composite molecule. As stronger hydrogen bond action exists between the two carbon acyl diamine groups formed by condensation in the composite molecule, stronger hydrogen bond action exists between the composite molecules, and the composite molecule has the self-repairing characteristic through the hydrogen bond action between the composite molecules. On one hand, the molecules in the adhesive have high elasticity, a high-elasticity space is formed on the surfaces of the electrode active material and the conductive agent, the tight combination between the electrode materials is kept, and the electrode materials are prevented from falling off; on the other hand, association is generated between molecules and in the molecules through hydrogen bonds between self-repairing molecular chains, so that the self-repairing molecules form a three-dimensional network structure, the capability of the binding agent for capturing fragments of the electrode active material is enhanced, and the electrochemical properties of the battery, such as stability, safety and the like, are improved.
In some embodiments, the amino-terminated polymer is selected from: at least one of amino-terminated polyethylene glycol and amino-terminated polyvinyl alcohol. The amino-terminated polyethylene glycol and the amino-terminated polyvinyl alcohol in the embodiment of the invention have higher viscosity, so that the adhesive has proper adhesive property. In some embodiments, the amino-terminated polyethylene glycol has an average molecular weight of 400 to 100000. In other embodiments, the amino-terminated polyvinyl alcohol has an average molecular weight of 400 to 100000. With the increase of the molecular weight of the polymer, the viscosity of the binder is higher under the same concentration, and the amino-terminated polymer with proper molecular weight and the diisocyanate modified monomer can be reasonably selected as raw materials to prepare the binder according to the requirement of the actual situation on the viscosity of the binder, so that the flexibility is high, and the adaptability is wide.
In some embodiments, the diisocyanate-modified monomer is selected from the group consisting of: 1,3-diisocyanato, hexamethylene diisocyanate, p-phenylene diisocyanate and isophorone diisocyanate, wherein the monomers contain two isocyanate groups and can perform condensation reaction with amino-terminated polymers to generate composite molecules containing carbonyl diamine groups, and the carbonyl diamine groups have strong hydrogen bonding effect among the composite molecules, so that the composite molecules have self-repairing property, can adapt to volume change in the electrode charge and discharge process and prevent electrode materials from falling off; moreover, self-repairing molecules form a three-dimensional network structure through hydrogen bond association between self-repairing molecular chains, and the capability of the binding agent for capturing fragments of the electrode active material is enhanced, so that the electrochemical properties of the battery, such as stability, safety and the like, are improved.
In some embodiments, the organic solvent is selected from: at least one of dimethylacetamide, N-dimethylformamide, acetone and chloroform, and the organic solvents have good solubility characteristics on polymers of terminal amino groups and diisocyanate modified monomers, so that a solvent system is provided for the condensation reaction between the polymers and the monomers.
In some embodiments, the mass ratio of the amino-terminated polymer to the diisocyanate-modified monomer is (8-12): the amino-terminated polymer and the diisocyanate modified monomer are dissolved in an organic solvent, the amino-terminated polymer and the diisocyanate modified monomer in the mass ratio ensure the content of the carbodiimide groups in the self-repairing molecules generated after condensation, so that the hydrogen bond acting force between the self-repairing molecules can endow the adhesive with strong self-repairing characteristics, and the raw material utilization rate is high. In some embodiments, the amino-terminated polymer and the diisocyanate-modified monomer are present in a mass ratio of 8: 1. 9: 1. 10: 1. 11:1 or 12: dissolving the amino-terminated polymer and the diisocyanate-modified monomer in an organic solvent.
In some embodiments, the amino-terminated polymer and the diisocyanate-modified monomer are dissolved in an organic solvent and then reacted at a temperature of 70 ℃ to 90 ℃ for 10 hours or more, under which the amino-terminated polymer and the diisocyanate-modified monomer are capable of undergoing a dehydration condensation reaction, and the sufficiency of the condensation reaction is ensured by reacting for 10 hours or more.
In some embodiments, after mixing the organic solution of the amino-terminated polymer and the organic solution of the diisocyanate-modified monomer to form a mixed solution, reacting at a temperature of 70 ℃ to 90 ℃ for more than 10 hours; in the mixed solution, the mass ratio of the amino-terminated polymer to the diisocyanate-modified monomer is (8-12): 1. according to the embodiment of the invention, the polymer with the amino end is dissolved in the organic solvent to form the organic solution in advance, the monomer modified by the diisocyanate is dissolved in the organic solvent to form the solution, the two are mixed to form the mixed solution and then subjected to condensation reaction, so that the polymer and the monomer can be subjected to contact reaction more fully and uniformly, the progress of condensation polymerization reaction is accelerated, and the stability of the reaction is improved.
In some embodiments, amino-terminated polyethylene glycol and 1,3-diisobenzonitrile are used as raw materials, and are dissolved in an organic solvent to perform a mixing reaction, so as to obtain the following self-repairing molecules:
wherein x varies with the average molecular weight of the amino-terminated polyethylene glycol, and is larger when the average molecular weight of the amino-terminated polyethylene glycol is larger, and correspondingly smaller when the average molecular weight of the amino-terminated polyethylene glycol is smaller.
Specifically, in step S20, a dispersion of a carbon material is obtained, the dispersion of the carbon material and the solution of the self-repairing molecules are mixed, and then heat treatment is performed, and drying is performed to obtain an aqueous binder solid product; wherein the carbon material contains an active group capable of being connected with the self-repairing molecule. In the embodiment of the invention, the carbon material and the self-repairing molecules can be fully reacted, the functionalized carbon material with poor dispersibility is pre-dispersed in a solvent to obtain a dispersion liquid, then the dispersion liquid of the carbon material and the solution of the self-repairing molecules are fully and uniformly mixed, then heat treatment is carried out to enable active groups on the self-repairing molecules to be subjected to condensation reaction with functionalized active groups on the carbon material, the self-repairing molecules are known on the carbon material to generate a water-based binder, and finally the solvent in a reaction system is removed and dried to obtain a water-based binder solid product. The aqueous binder solid product is convenient to transport and store, can be adjusted into aqueous binder slurry with proper viscosity by adding water when in use, and is flexible and convenient to apply.
In some embodiments, the carbon material comprises: the carbon nano tube, the graphene, the carbon fiber and other carbon materials have larger comparative area, can coat active substances in the electrode slurry, can further inhibit the electrode active materials from volume expansion in the charging and discharging processes of the battery, and improves the strength of electrode plates and the electron transmission capacity in the electrode plates, thereby improving the cycle stability of the battery and prolonging the service life of the battery.
In some embodiments, the reactive group comprises: at least one of hydroxyl and carboxyl, and active groups such as hydroxyl and carboxyl grafted on the surface of the carbon material can be subjected to condensation reaction with active groups such as hydroxyl in self-repairing molecules, so that the self-repairing molecules are grafted on the surface of the carbon material to form the composite material of the water-based binder.
In some embodiments, the solvent in the dispersion of carbon material comprises: the functionalized carbon material has better dispersibility in the organic solvents, and the organic solvents also have better solubility to self-repairing molecules, thereby being beneficial to the condensation polymerization reaction of the carbon material and the self-repairing molecules.
In some embodiments, the functional carbon material and the self-repairing molecule are mixed in a mass ratio of (1-10): (90-99) mixing the dispersion liquid of the carbon material with the solution of the self-repairing molecules, wherein the mass content of the carbon material in the aqueous binder generated by condensing the carbon material and the self-repairing molecules in the mass ratio is 1-10%, the percentage content of the carbon material has the best balance on the rigidity and the conductivity of the binder and on the volume expansion inhibition effect of an electrode active substance, and if the content of the carbon material is too low, the modification effect on the binder is not good; if the content of the carbon material is too low, the viscosity of the binder is lowered, the moldability is lowered, and the force acting between the electrode active slurry and the current collector is lowered. In some embodiments, the ratio of the mass of the functional carbon material to the mass of the self-repairing molecule is (2-5): (95-98) mixing the dispersion of the carbon material with the solution of the self-repairing molecules, wherein the carbon material has a better balance effect on the viscosity, rigidity, conductivity of the binder and the volume expansion inhibition effect of the electrode active material.
In some embodiments, the carbon material dispersion and the self-repairing molecule solution are mixed and then reacted at a temperature of 110 ℃ to 130 ℃ for 60 minutes or more, so that the carbon material and the self-repairing molecule are fully contacted to perform a condensation reaction, and an aqueous binder is generated.
In some embodiments, the functional carbon material and the self-repairing molecule are mixed according to the mass ratio of (1-10): (90-99), adding the dispersion liquid of the carbon material into the solution of the self-repairing molecules under stirring, and then reacting at the temperature of 110-130 ℃ for more than 60 minutes to fully contact the carbon material with the self-repairing molecules to perform condensation reaction to generate the water-based binder.
In some embodiments, the viscosity of the aqueous binder slurry formed upon dissolving the aqueous binder solid product in water ranges from 1000 to 10000mpa.s. The aqueous binder prepared by the embodiment of the invention has adjustable square width of the viscosity of the binder slurry formed by adding water, can be suitable for different battery systems, meets the requirement of electrode preparation conditions on the viscosity of the binder, and has flexible and convenient application and wide application range.
In some embodiments, the weight ratio of amino terminated polyethylene glycol to 1,3-diisothiocyanate is 10:1, dissolving the self-repairing molecular compound in at least one organic solvent of dimethylacetamide, N-dimethylformamide, acetone and chloroform, and reacting at 70-90 ℃ for more than 10 hours to obtain a self-repairing molecular solution; then, dropping an organic dispersion liquid of graphene containing hydroxyl and/or carboxyl into a solution of self-repairing molecules under stirring, wherein the mass ratio of the graphene containing hydroxyl and/or carboxyl to the self-repairing molecules is (1-10): (90-99) reacting at 110-130 deg.C for more than 60min, and drying to obtain water-based binder shown in figure 1.
Correspondingly, the embodiment of the invention also provides a lithium ion battery negative plate, which comprises the aqueous binder prepared by the method, or comprises the aqueous binder.
The lithium ion battery negative plate provided by the embodiment of the invention contains the aqueous binder which has proper viscosity, rigidity and conductivity and has an inhibiting effect on the volume expansion of the electrode active substance, so that the strength of the lithium ion battery negative plate is improved, the electron transmission capability in the plate is improved, and the safety and the cycle stability of the battery are improved.
In some embodiments, the negative active material in the negative electrode sheet of the lithium ion battery comprises at least one of a graphite material, a silicon-based material and a silicon-carbon composite material; the silicon-based material is one of nano silicon, micron silicon, porous silicon, amorphous silicon and a silicon monoxide material.
In some embodiments, the mass ratio of the aqueous binder to the negative active material and the conductive agent in the material of the lithium ion battery negative electrode sheet is (5-20): (50-80): (10-30).
In some embodiments, the conductive additive is at least one of acetylene black, super electric black, ketjen black, graphene, carbon nanotubes, carbon fibers.
In some embodiments, the preparation of the negative electrode sheet of the lithium ion battery comprises the steps of: the mass ratio of the water-based binder to the negative electrode active material to the conductive agent is (5-20): (50-80): (10-30), uniformly mixing the negative active material and the conductive additive, adding a proper amount of deionized water to adjust the viscosity of the slurry, and fully mixing to obtain slurry; then uniformly coating the slurry on a copper foil; and drying to obtain a pole piece, and then placing the pole piece in a vacuum drying oven at 60 ℃ for full drying to obtain the lithium ion battery negative pole piece.
Correspondingly, the embodiment of the invention also provides a lithium ion battery, and the lithium ion battery comprises the aqueous binder or the lithium ion battery negative plate.
The lithium ion battery provided by the embodiment of the invention contains the aqueous binder which has proper viscosity, rigidity and conductivity and has an effect of inhibiting the volume expansion of the electrode active material, or contains the lithium ion battery negative plate with excellent stability, strength and electron transmission capability, so that the provided lithium ion battery has good safety, good cycle stability and long service life.
In order to make the above-mentioned implementation details and operation of the present invention clearly understood by those skilled in the art and to make the progress of the water-based adhesive prepared by the embodiments of the present invention apparent, the above-mentioned technical solutions are exemplified by a plurality of examples and test examples below.
Example 1
The effect of different average molecular weight aminated polyethylene glycols on the viscosity of the aqueous binder prepared was examined.
Respectively dissolving 200mg of amino-terminated polyethylene glycol with average molecular weights of 400, 6000, 20000 and 80000 in N, N-dimethylformamide to prepare a solution with a concentration of 5wt%, dispersing 15mg of 1,3-diisobenzonitrile ester in N, N-dimethylformamide to prepare a solution with a concentration of 5wt%, and reacting at 80 ℃ for 12 hours to obtain N, N-dimethylformamide solutions of self-repairing molecules with different molecular weights;
dispersing 10mg of carboxylated carbon nanotubes in 10mL of N, N-dimethylformamide to be uniformly dispersed, dropwise adding the mixture into a self-repairing high molecular solution while stirring, reacting for 60min at 50 ℃ to obtain a compound, and drying to obtain water-system binder solid products with different molecular weights;
the prepared water-based binder solid products with different molecular weights are dissolved in water with the same volume, and the influence of the aminated polyethylene glycol with different molecular weights on the viscosity of the binder is compared.
As shown in fig. 2, the viscosity of the binder at the same concentration is higher as the average molecular weight of the aminated polyethylene glycol is increased, so that water-based binders meeting different application requirements can be prepared by selecting the average molecular weight of the aminated polyethylene glycol, and the application is flexible and convenient.
Example 2
The influence of grafting to different carbon materials on the electronic conductivity of the water-based binder was examined.
The self-repairing molecules polymerized by the amino-terminated polyethylene glycol with the average molecular weight of 6000 and 1,3-diisobenzonitrile, and the carboxylated graphene, the carboxylated carbon nanotubes and the carboxylated carbon fibers were respectively mixed to prepare the aqueous binder with the carbon material content of 5wt% according to the preparation method of example 1.
The resistivity and the conductivity of the prepared water-based adhesive of different carbon material substrates were tested, and as shown in table 1 below, under the same conditions, when graphene and carbon nanotubes are used as a grafting substrate, the water-based adhesive shows better conductivity, and the conductivity reaches 0.822S/cm, while when carbon fibers are used as the grafting substrate, the conductivity of the adhesive is slightly inferior.
TABLE 1
| Resistivity (m omega cm) | Conductivity (S/cm) | |
| Carboxylated graphene | 978 | 0.822 |
| Carboxylated carbon nanotube | 1020 | 0.736 |
| Carboxylated carbon fiber | 1660 | 0.082 |
Example 3
And (3) investigating the influence of water-based binders with different carbon material contents on the viscosity/stripping performance of the battery pole piece.
Self-repairing molecules formed by polymerizing amino-terminated polyethylene glycol with the average molecular weight of 6000 and 1,3-diisobenzonitrile, and carboxylated graphene are used for preparing the water-based binder with the graphene contents of 1wt%,2wt%,3wt%,5wt%,7wt% and 10wt% according to the preparation steps of example 1.
And mixing the silicon-based negative electrode, the conductive carbon black and the water-based binder according to the weight ratio of 8:1:1, adding deionized water to adjust the concentration of the slurry, fully mixing, pulping, coating on a copper foil, drying at room temperature, drying in a 60 ℃ drying oven for 12 hours, and rolling the dried electrode plate to obtain the silicon-based negative electrode plates with different carbon material contents.
Under the condition of controlling the same compaction density, the peel force test is carried out on the prepared silicon-based negative electrode plates with different carbon material contents, and the test result is shown in fig. 3, wherein the smaller the peel force of the electrode plate is along with the increase of the carbon content in the binder, which shows that the increase of the rigidity of the binder can reduce the film forming property and the viscosity of the binder, so that the acting force between the electrode plate and a current collector is reduced.
Example 4
A half-cell assembled by a silicon-based negative electrode plate prepared by using the aqueous binder containing 5wt% of graphene in example 3 and metallic lithium was relatively assembled, and the influence of the half-cell on the silicon-carbon performance was studied.
Cutting the electrode plate into a wafer with the diameter of 10mm and the active substance loading capacity of 1.5mg/cm 2 The cathode adopts a lithium sheet with the diameter of 12mm, a 2032 button battery is assembled, and the electrolyte adopts 1MLiPF 6 1 in a volume ratio of 1In an EC/DMC/DEC solvent, standing for 6 hours after the battery is assembled, and performing a constant-current charge-discharge test in a blue-ray test system, wherein the voltage range is 0.01-2V, as shown in FIG. 4, the first-cycle discharge capacity is 870mAh/g, the first-cycle charge capacity is 692mAh/g, the first effect is 79%, and the charge-discharge curve is normal, which indicates that the water-based binder prepared by the embodiment of the invention can normally work in the battery.
Example 5
A silicon-based negative electrode sheet prepared with the aqueous binder having a graphene content of 5wt% in example 3 was matched with NCM622 to assemble a full cell, where n/p =1.05. Positive plate was as NCM622: and (3) SuperP: PDVF =8:1:1, mixing, pulping by taking NMP as a dispersant, uniformly coating on a carbon-coated aluminum foil, drying at 60 ℃, placing in a vacuum oven at 80 ℃ for drying for 12 hours, and then cutting into a solution to study the influence of the solution on the performance of silicon and carbon. Cutting the electrode plate into a circular sheet with the diameter of 10mm, assembling a 2032 button cell, and adopting 1MLiPF as electrolyte 6 The lithium ion battery is dissolved in an EC/DMC/DEC solvent with a volume ratio of 1.
The above description is intended to be illustrative of the preferred embodiment of the present invention and should not be taken as limiting the invention, but rather, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.
Claims (8)
1. A preparation method of a water-based binder is characterized by comprising the following steps:
obtaining an amino-terminated polymer and a diisocyanate modified monomer, wherein the mass ratio of the amino-terminated polymer to the diisocyanate modified monomer is (8-12): 1, dissolving the amino-terminated polymer and the diisocyanate modified monomer in an organic solvent, and then carrying out mixed reaction for more than 10 hours at the temperature of 70-90 ℃ to obtain a self-repairing molecule containing a carbonyl diamine group; the self-repairing molecular chains form a three-dimensional network structure through hydrogen bond association;
obtaining a dispersion liquid of a carbon material, wherein the mass ratio of the carbon material to the self-repairing molecules is (2-5): (95-98) mixing the dispersion of the carbon material with the solution of the self-repairing molecules, performing heat treatment, and drying to obtain a water-based binder solid product;
wherein the carbon material contains an active group capable of being connected with the self-repairing molecule; the viscosity of the aqueous binder slurry formed by dissolving the aqueous binder solid product in water is in the range of 1000 to 10000mPa.s.
2. The method for producing an aqueous binder according to claim 1, wherein the amino-terminated polymer is selected from the group consisting of: at least one of amino-terminated polyethylene glycol and amino-terminated polyvinyl alcohol; and/or the presence of a gas in the gas,
the diisocyanate modified monomer is selected from: 1,3-diisocyanatobenzene, hexamethylene diisocyanate, p-phenylene diisocyanate, isophorone diisocyanate; and/or the presence of a gas in the atmosphere,
the organic solvent is selected from: at least one of dimethylacetamide, N-dimethylformamide, acetone and chloroform.
3. The method for producing an aqueous binder according to claim 2, wherein the amino group-terminated polyethylene glycol has an average molecular weight of 400 to 100000; and/or the presence of a gas in the gas,
the average molecular weight of the amino-terminated polyvinyl alcohol is 400-100000; and/or the presence of a gas in the gas,
the carbon material includes: at least one of carbon nanotubes, graphene and carbon fibers; and/or the presence of a gas in the atmosphere,
the reactive group includes: at least one of a hydroxyl group and a carboxyl group; and/or the presence of a gas in the gas,
the solvent in the dispersion of the carbon material includes: at least one of dimethylacetamide, N-dimethylformamide, acetone and chloroform.
4. The method for producing an aqueous binder according to claim 3, wherein the heat treatment conditions include: reacting for more than 60 minutes at the temperature of 110-130 ℃.
5. The aqueous binder prepared by the method according to any one of claims 1 to 4, wherein the aqueous binder comprises a carbon material and self-repairing molecules grafted on the surface of the carbon material, and the self-repairing molecules are prepared by condensation reaction of an amino-terminated polymer and a diisocyanate-modified monomer.
6. The water-based adhesive according to claim 5, wherein the amino-terminated polymer is selected from the group consisting of: at least one of amino-terminated polyethylene glycol and amino-terminated polyvinyl alcohol; and/or the presence of a gas in the gas,
the average molecular weight of the amino-terminated polymer is 400-100000; and/or the presence of a gas in the gas,
the diisocyanate modified monomer is selected from: 1,3-diisocyanatobenzene, hexamethylene diisocyanate, p-phenylene diisocyanate, isophorone diisocyanate; and/or the presence of a gas in the atmosphere,
the carbon material includes: at least one of carbon nanotubes, graphene, carbon fibers; and/or the presence of a gas in the gas,
in the aqueous binder, the mass percentage content of the carbon material is 1-10%.
7. A negative electrode sheet for a lithium ion battery, comprising the aqueous binder prepared by the method according to any one of claims 1 to 4, or comprising the aqueous binder according to any one of claims 5 to 6.
8. A lithium ion battery comprising the aqueous binder prepared by the method of any one of claims 1 to 4, or comprising the aqueous binder of any one of claims 5 to 6, or comprising the negative electrode sheet of the lithium ion battery of claim 7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010036091.XA CN113130897B (en) | 2020-01-14 | 2020-01-14 | Water-based binder and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010036091.XA CN113130897B (en) | 2020-01-14 | 2020-01-14 | Water-based binder and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113130897A CN113130897A (en) | 2021-07-16 |
| CN113130897B true CN113130897B (en) | 2022-10-21 |
Family
ID=76771185
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010036091.XA Active CN113130897B (en) | 2020-01-14 | 2020-01-14 | Water-based binder and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113130897B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113690440B (en) * | 2021-07-30 | 2023-01-10 | 深圳市研一新材料有限责任公司 | Electrode slurry composition, pole piece and secondary battery thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015122498A1 (en) * | 2014-02-13 | 2015-08-20 | 東ソー株式会社 | Hydrophilic polymer, production method for same, binder, electrode |
| CN105161720A (en) * | 2015-09-22 | 2015-12-16 | 安徽大学 | Lithium-ion battery anode sizing agent based on waterborne polyurethane bonder |
| CN105153905A (en) * | 2015-07-03 | 2015-12-16 | 泰山玻璃纤维有限公司 | Preparation method and application of graphene modified polyurethane film-forming agent |
| CN106700013A (en) * | 2016-11-07 | 2017-05-24 | 苏州大学 | Strong polar polymer adhesive as well as synthesis method and application thereof in lithium battery |
| CN109461937A (en) * | 2018-10-19 | 2019-03-12 | 深圳市优宝新材料科技有限公司 | A kind of lithium battery three-dimensional hybrid conductive adhesive and include the battery of the binder |
| CN110034279A (en) * | 2019-05-08 | 2019-07-19 | 福州大学 | A kind of preparation method of flexible lithium ion battery negative electrode material |
| CN110061238A (en) * | 2018-03-20 | 2019-07-26 | 南方科技大学 | Water-soluble self-healing binder and preparation method thereof and lithium ion battery |
-
2020
- 2020-01-14 CN CN202010036091.XA patent/CN113130897B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015122498A1 (en) * | 2014-02-13 | 2015-08-20 | 東ソー株式会社 | Hydrophilic polymer, production method for same, binder, electrode |
| CN105153905A (en) * | 2015-07-03 | 2015-12-16 | 泰山玻璃纤维有限公司 | Preparation method and application of graphene modified polyurethane film-forming agent |
| CN105161720A (en) * | 2015-09-22 | 2015-12-16 | 安徽大学 | Lithium-ion battery anode sizing agent based on waterborne polyurethane bonder |
| CN106700013A (en) * | 2016-11-07 | 2017-05-24 | 苏州大学 | Strong polar polymer adhesive as well as synthesis method and application thereof in lithium battery |
| CN110061238A (en) * | 2018-03-20 | 2019-07-26 | 南方科技大学 | Water-soluble self-healing binder and preparation method thereof and lithium ion battery |
| CN109461937A (en) * | 2018-10-19 | 2019-03-12 | 深圳市优宝新材料科技有限公司 | A kind of lithium battery three-dimensional hybrid conductive adhesive and include the battery of the binder |
| CN110034279A (en) * | 2019-05-08 | 2019-07-19 | 福州大学 | A kind of preparation method of flexible lithium ion battery negative electrode material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113130897A (en) | 2021-07-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Lingappan et al. | The significance of aqueous binders in lithium-ion batteries | |
| WO2018000579A1 (en) | Multifunctionalized modified polymer binder for lithium ion battery and use thereof in electrochemical energy storage device | |
| CN110148751B (en) | Silicon-carbon cathode and preparation method thereof | |
| WO2018000578A1 (en) | Multi-functional modified polyvinyl alcohol-based water-borne adhesive for lithium ion battery and application thereof in electrochemical energy storage device | |
| CN109698354B (en) | Binder, negative electrode slurry using binder, and preparation method and application of negative electrode slurry | |
| Kuo et al. | In situ cross-linked poly (ether urethane) elastomer as a binder for high-performance Si anodes of lithium-ion batteries | |
| CN110323445B (en) | PAA-CA complex phase binder and preparation method thereof | |
| CN110190284B (en) | Water-based binder for lithium-sulfur battery positive electrode and preparation method and application thereof | |
| CN114744200B (en) | Ionic crosslinked polymer, conductive adhesive, and preparation method and application thereof | |
| CN111106352A (en) | Cross-linking type water-based binder for lithium ion battery and electrode prepared from cross-linking type water-based binder | |
| CN113659145A (en) | Cathode slurry and preparation method thereof, and lithium ion battery and preparation method thereof | |
| Wu et al. | Ionic network for aqueous-polymer binders to enhance the electrochemical performance of Li-Ion batteries | |
| CN109728303B (en) | Water-based conductive binder suitable for silicon-based negative electrode material of lithium ion battery and preparation method thereof | |
| Xiong et al. | SiO x-based graphite composite anode and efficient binders: practical applications in lithium-ion batteries | |
| CN111647345A (en) | Lithium ion battery negative electrode polymer protective coating and preparation method and application thereof | |
| CN113130897B (en) | Water-based binder and preparation method and application thereof | |
| CN111406331A (en) | Method for producing slurry for nonaqueous battery electrode | |
| CN110492101B (en) | Lithium ion battery cathode binder and preparation method and application thereof | |
| CN117089017A (en) | Non-fluorine binder for positive electrode of lithium ion battery, positive electrode using same and battery | |
| CN116731635A (en) | Conductive adhesive and preparation method and application thereof | |
| CN116247214A (en) | Dispersing auxiliary, preparation method and application thereof | |
| KR101923058B1 (en) | High dielectric polymer composite composition and energy storage device using same | |
| CN114156471B (en) | Graphite negative electrode material and preparation method and application thereof | |
| CN114284497A (en) | Water-based self-healing adhesive and preparation method thereof | |
| CN108695508B (en) | High-energy lithium battery negative electrode slurry and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |